Aliphatic polysulfones with improved mechanical integrity

ABSTRACT

A polysulfone has sulfone units that are separated by alkylene units in a polymer chain or a copolymer chain where the alkylene units have at least four carbons between sulfone units. The alkylene units can include an ethenylene unit separated from the sulfone units by at least one methylene units. The polysulfones can be crosslinked for enhanced thermal stability. Membranes can be formed from the polysulfones.

CROSS-REFERENCE TO A RELATED APPLICATION

This application is a Continuation-in-Part of U.S. patent applicationSer. No. 16/304,433, filed on Nov. 26, 2018, which was a 371 ofPCT/US2017/034621 filed on May 26, 2017 claiming the benefit of U.S.Provisional Application Ser. No. 62/341,787, filed May 26, 2016, thedisclosures of which are hereby incorporated by reference in theirentirety, including all figures, tables and drawings.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under Grant No.W911NF-13-1-0362 awarded by the Office of Army Research. The governmenthas certain rights in the invention.

BACKGROUND OF INVENTION

Polysulfone is a term that has become synonymous with aryl sulfones.Commercial polysulfones are known for their excellent chemical andthermal stability. Polysulfones possess a superior service temperaturerange (150-200° C.) and good mechanical properties. Polysulfones oftenare used when polycarbonates and other engineering plastics cannotwithstand conditions required. Sulfone functionalities add a polarfeature to polymers and, unlike polyesters, polysulfones are resistantto acid and base hydrolysis. These features allow these thermoplasticpolysulfone materials to find many high-end applications in theaerospace, medical, and automotive industries, and for consumer goodsand machine parts.

Random aliphatic polysulfones are not as prevalent as their amorphous,rigid-rod, aromatic counterparts. Aliphatic sulfone copolymers aretypically produced through free-radical polymerization of SO₂ andolefins, and these resulting polymers are stable to temperatures ofaround 200-225° C. However, these polymers have limited use due to theircost of production and because of undesirable structural defects, suchas uncontrollable branching incurred during free-radical polymerization.

Faye et al., J. Polym. Chem. 2014, 5, (7), 2548-60, used acyclic dienemetathesis (ADMET) polymerization to study the crystalline nature ofaromatic etherethersulfone copolymers. ADMET polymerization has beencarried out in the presence of oxidized sulfur functionalities,sulfonate esters, sulfonic acids, sodium salts, and sulfites or theirsulfur containing precursors. ADMET polymerization yields precisestructures, which often permit more viable materials. Polymerssynthesized via ADMET exhibit better crystalline and thermal properties.Sulfone-ADMET compatibility could, therefore, allow production oflinear, aliphatic polysulfones. To this end a precisely formed aliphaticpolysulfone is desired.

BRIEF SUMMARY

In an embodiment of the invention, a polysulfone comprises sulfone unitsseparated by alkylene units in a homopolymer chain or a copolymer chain.The alkylene units can be of the same mass and structure or can be ofisomers of the same mass or oligomethylene units of different mass. Thealkylene unit can be C₄ to C₃₆ units. The alkylene units can include anethenylene unit such that it is separated from the sulfone units by atleast one methylene unit. The polysulfone can be a crosslinked gel whereon average at least two alkylene units of each homopolymer or copolymerchain or copolymer chain comprise a crosslinking unit between at leasttwo polymer chains or copolymer chains. Crosslinks can be the reactionproduct of an ethenylene unit with a diacrylate or a dithiol or anethenylene unit converted to an epoxy unit with a diol or a diamine.

Another embodiment of the invention is directed to a method of preparinga polysulfone where a monomer mixture of at least oneα,ω-bis-vinylalkylsulfone monomer and/or a cycloalkenylsulfone withdouble bonds separated from the sulfone by at least one methylene unitare combined in a solvent is combined with a metathesis catalyst toinitiate polymerization with the removal of ethylene to form a polymercomprising a multiplicity of sulfone units separated by alkenylene unitswhere ethenylene units are separated from the sulfone units by at leastone methylene unit. Optionally, at least a portion of the ethenyleneunits can be reduced to ethylene units. Optionally, a portion of theethenylene units can be used to form crosslinking units.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows aliphatic polysulfones with sulfone units situated every8_(th), 14_(th), and 20^(th) methylene unit according to an embodimentof the invention.

FIG. 2 shows a reaction schematic for the preparation of anα,ω-bis-vinylalkylsulfone, the ADMET polymerization to theα,ω-bis-vinylalkylsulfone, and the hydrogenation of thepoly(α,ω-bis-vinylalkylsulfone) to a polysulfone.

FIG. 3A shows a reaction scheme for a one-pot preparation ofbis(pent-4-en-1-yl)sulfone.

FIG. 3B shows the ¹H NMR for the protons ω to α (A through F) ofbis(pent-4-en-1-yl)sulfone prepared by the one-pot synthesis of FIG. 3A.

FIG. 4 shows composite ¹H NMR spectra with labeled signals (CDCl₃) forthe α,ω-bis-vinylalkylsulfone with six methylene units per arm (A); theunsaturated polysulfone formed by ADMET polymerization (C₂D₂Cl₄) (B) andthe saturated aliphatic polyalkanylsulfone (C₂D₂Cl₄) (C).

FIG. 5 shows a reaction schematic for the preparation of apoly(α,ω-bis-vinylalkylsulfone) by the solventless ADMET polymerizationof bis(pent-4-en-1-yl)sulfone, according to an embodiment of theinvention.

DETAILED DISCLOSURE

Embodiments of the invention are directed to periodic, quasiperiodic,and quasirandom linear poly(alkanylsulfones), linearpoly(alkenylsulfones), crosslinked poly(alkanylsulfones) and crosslinkedpoly(alkenylsulfones). Other embodiments of the invention are directedto, their preparation, and membranes or other devices therefrom. Thestructure of some polyalkenylsulfones, according to an embodiment of theinvention, is shown in FIG. 1. The (alkanylsulfones), linearpoly(alkenylsulfones), crosslinked poly(alkanylsulfones) and crosslinkedpoly(alkenylsulfones) can be prepared by the acyclic diene metathesis(ADMET) polymerization of one or more α,ω-bis-vinylalkylsulfones, whereat least one methylene unit separates the terminal ene groups from thesulfone unit within the methylene units. Preparation andhomopolymerization of α,ω-bis-vinylalkylsulfones are shown in FIG. 2.Subsequent hydrogenation of the ene units in the resulting aliphaticpolysulfones is also shown in FIG. 2. Carrying out one or a series ofreactions with the ene units within the poly(alkenylsulfone)s allows theformation of a structure that can be used in a membrane form or that hasenhanced utility at temperatures of up to 200° C. or more. Thepolymerization of the monomer can be carried out using any knownmetathesis catalyst, for example, Schrock's catalyst(Mo(═CHCMe₂Ph)(N-2,6-C₆H₃-i-Pr₂)(OCMe(CF₃)₂)₂), Grubbs' first generationcatalyst (RuCl₂(═CHPh)(PCy₃)₂), or Grubbs' second generation catalyst(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene) (tricyclo-hexylphosphine)ruthenium.Alternatively, ring-opening metathesis polymerization (ROMP) can beperformed using one or more cycloalkenylsulfones where at least onemethylene unit separates the ene from the sulfonyl unit. Generally, thecycloalkenylsulfone is smaller than an eight membered ring, which limitsthe separation of sulfonyl units along the chain. With even-numberedring sizes, the sulfonyl units cannot be placed with equi-sizedmethylene sequences along the chain. Hence, for practical purposes, theseven-membered ring is about the largest functionalized cycloalkene thatcan result in a periodic placement of functional groups, which leads toa practical maximum of only six methylene units separating the sulfonylunits within the resulting polymer from ring-opening ofcycloalkenylsulfones.

The preparation of the α,ω-bis-vinylalkylsulfone monomer can be carriedout as shown in FIG. 2. The monomer can be prepared in two steps througha sulfide intermediate, as shown in FIG. 2, where x is the number ofmethylene groups in the monoene reagent and is the same or different,and is 1 to 20 or more. When x is the same value, the resultingsymmetric monomer can be used to prepare a polymer that is periodic.Alternatively, as shown in FIG. 3A for the α,ω-bis-vinylpropylsulfone,characterization by ¹HNMR shown in FIG. 3B, monomers can be prepared ina single step from sodium hydroxymethylsulfinate and ω-halo-α-alkenes.

When x is different, for example, an asymmetricα,ω-bis-vinylalkylsulfone monomer having an x and a y value that aredifferent, a “quasiperiodic” polymer can be formed where the separatingmethylene units in the substituted polyethylene can be only 2x+2, 2y+2,and x+y+2 in a 1:1:2 ratio but no other values are possible.Alternatively, by employing two symmetric α,ω-bis-vinylalkylsulfones,one with two x length sequences and one with two y length sequences, oran asymmetric x and y monomer and a symmetric x and x monomer, therepeating unit sequences between functionalized methylenes of theultimate substituted polyalkenylsulfone can be only 2x+2, 2y+2, andx+y+2, but the ratio of these units can differ from a 1:1:2 ratio andthe longer range order will be different from that where there is asingle asymmetric monomer. By tailoring the sequence lengths, forexample, where the values of x and y are sufficiently similar, forexample, x is about 1.05y to about 1.2y, or the proportion of ysequences is small, the disruption from periodicity may not prohibit adesired organization of the polymer into desired associations of thepolymers. For example, in a membrane similar to that using periodicpolymers, by promoting defects from periodicity, the processes oforganization can be kinetically enhanced by the structural defects withlittle penalty in the ultimate organized structure.

A “quasirandom” structure can occur where more than two x sequencelengths are employed. For example, x, y and z sequences can be formedwhen at least two α,ω-bis-vinylalkylsulfone monomers and with at leastone being asymmetric, or when three monomers of any type are employed.Inherently, the method employed for preparation of the polymers does notpermit a sequence between sulfone units of less than four methyleneunits; a truly random copolymer is not possible with these monomers.Alternatively, monomers with a plurality of sulfone groups separated bysized methylene sequences could be constructed that could ultimately becombined alone or with α,ω-bis-vinylalkylsulfone monomers to generatewhat approximates truly random polysulfones.

The α,ω-bis-vinylalkylsulfone monomers can include alkylene sequencesthat are branched or substituted. The α,ω-bis-vinylalkylsulfone monomerscan be copolymerized with C₅ to C₂₀ α,ω-alkyldiene monomers orcycloalkane monomers to give random copolymers where the carbon chainsare extended between sulfone units. The α,ω-bis-vinylalkylsulfonemonomers can be copolymerized with α,ω-bis-vinylalkylsulfides.

After ADMET or ROMP polymerization, the poly(α,ω-bis-vinylalkylsulfone)can be reduced to the polysulfone, as shown in FIG. 2. Hydrazidereduction, for example, with toluenesulfonylhydrazide (TSH), can becarried out in solution in the presence of a trialkylamine The reductioncan be carried out with effectively complete conversion of the olefinusing an excess of the hydrazide, or a controlled degree of reduction ispossible by using a deficiency of the hydrazide. As indicated in FIG. 4,the reduction is easily followed by analytical methods, including, butnot limited to, ¹H NMR spectroscopy.

The ADMET polymerization is carried out in solution at reflux to promotethe increase of molecular weight by the loss of ethylene. The solventcan be a low boiling solvent, such as methylene chloride, or a higherboiling solvent, such as, but not limited to, 1,2-dichloroethane,1,1,2,2,-tetrachloroethane, toluene, xylenes, ethyl acetate, and THF.Polymers prepared in methylene chloride using Grubbs' First Generationcatalyst are indicated in Table 1, below.

TABLE 1 Molecular Weight and Thermal Properties of Poly(aliphaticsulfones) Sulfone/ Sulfone M_(w) 500 T_(m) ΔH T_(95%) Polymer^(a)(g/mol)^(b) carbons (° C.)^(c) (J/g) (° C.)^(d) Unsaturated SO₂8U 13,80062 113 32.5 302 SO₂14U 15,800 35 125 27.6 325 SO₂20U 4,800 25 131 37.7345 Saturated SO₂8 — 62 175 49.1 260 SO₂14 — 35 167 47.9 290 SO₂20 — 25147 91.4 277 ^(a)Unsaturated polymers provided by ADMET polymerizationsof 24 hr duration and indicated by the number carbons in the symmetricmonomer indicated with “U” for the unsaturated polymer uponpolymerization and the saturated polymer formed upon reduction;^(b)molecular weights determined by DOSY in C₂Cl₄D₂; ^(c)T_(m) obtainedfrom DSC at 10° C./min.; ^(d)5% decomposition determined from TGA at 10°C./min.

Grubb's catalyst (C668), Dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II),allows synthesis of polysulfones without solvent, as indicated in FIG.5, above the melting temperature of the polymer without olefinisomerization. Molecular weight measurements were made using HFIP GPC vspolystyrene standards. Using this solvent-free technique highermolecular weight polymer are possible, as indicated in Table 2, for thepolymerization of below.

TABLE 2 Polymerization of bis(pent-4-en-1-yl)sulfone using Grubb'scatalyst (C668) Molecular Reaction Temperature Mole Ratio catalystweight Sample time (hrs) ° C. to monomer M_(w) (g/mol) 53 42 150 0.00328,448 10 72 130 0.002 23,992 55 43 150 0.005 36,544

Post-ADMET polymerization, carbon-carbon double bonds can be reacted toprovide crosslinking. Reaction of between 0.1% and 35% of the doublebonds within polymer samples results in a significant improvement inmechanical properties. Crosslinking reactions that can be carried outwith the unsaturated polymers include, but are not limited to,free-radical reactions, olefin metathesis with triene molecules,epoxidation followed by addition of various hardeners, thiol-ene andother “click” reactions. Crosslinking can be carried out via: adiacrylate reacting with ADMET double bonds; a dithiol reaction withADMET double bonds; the epoxidation of the ADMET double bonds followedby diol or diamine addition; bromination of double bonds followed byreaction with a difunctional nucleophilic reagent; or by addition ofphoto reactive crosslinkers. Alternatively, high energy irradiation of adevice prepared from the reduced sulfone, for example, in the form of amembrane, can be carried out to crosslink and to stabilize the membrane.Such a crosslinked membrane, or other device, can be used as a componentof a fuel cell or a water desalination device.

Methods and Materials

Materials and Instrumentation

All chemicals, materials, and solvents were purchased through SigmaAldrich unless otherwise noted. Dry solvents where obtained from asolvent purification system when needed. Monomers were purified usingSiliCycle SiliaFlash® P60, 40-63 μm, 60 Å silica. Grubbs' 1st generationcatalyst was donated by Materia, Inc. and used as received. IRspectroscopy and data analysis was performed using a PerkinElmer FTIRSpectrum One with ATR attachment and Spectrum Software. A VarianMercury-300 NMR Spectrometer was used to obtain both 1H NMR and 13C NMRspectra using VNMRJ software. Due to the insolubility of polymers inmost solvents, DOSY NMR was performed on a Varian-500 NMR Spectrometerin deuterated tetrachloroethane at 25° C. Elemental analysis wasperformed by Atlantic Microlabs and mass spectroscopy was performed bythe Mass Spec labs in the University of Florida's Chemistry Department.

Synthetic Procedures

Bis(undec-10-en-1-yl)sulfide. A solution of 105 g (0.437 mols, 1.47 eq.)sodium sulfide nonahydrate was dissolved in 95 mL of 200 proof ethanol(˜0.2 mL/mmol of sodium sulfide nonahydrate) in a 500 mL round bottomflask. To this solution was added 70 g of 11-bromo-1-undecene (0.300mols, 1.0 eq.) and the reaction mixture was refluxed for 72 hours. Theflask was flooded with distilled water, stirred, and the product wasallowed to separate from the aqueous layer. The organic layer wasremoved and washed twice with a 5% sodium hydroxide solution, and oncewith water. The product was isolated as a yellow viscous oil, driedunder vacuum and used without further purification. Yield: 50.52 g,99.5%. ¹H NMR (300 MHz, CDCl₃): δ (ppm) 5.70-5.84 (m, 2H), 4.87-4.99 (m,4H), 2.49 (t, 4H), 1.96-2.03 (m, 4H), 1.74-1.84 (m, 4H), 1.17-1.43 (m,24H); ¹³C NMR (75 MHz, CDCl₃) δ 139.3, 114.3, 77.6, 77.2, 76.8, 34.0,32.4, 29.9, 29.7, 29.5, 29.3, 29.2, 28.9. Elemental Analysis: calcd forC₂₂H₄₂S, C: 78.03, H: 12.50, S: 9.47; found C: 78.19, H: 12.55, S: 9.58.

In like manner, the procedure described above was used for the synthesisof bis(oct-7-en-1-yl)sulfide and bis(pent-4-en-1-yl)sulfide as well.Spectra of all sulfides were consistent with published spectra.

Bis(oct-7-en-1-yl)sulfide. Yield: 80%. ¹H NMR (300 MHz, CDCl₃): δ (ppm)5.73-5.86 (m, 2H), 4.91-5.02 (m, 4H), 2.49 (t, 4H), 1.99-2.07 (m, 4H),1.57-1.62 (m, 4H), 1.26-1.43 (m, 12H); ¹³C NMR (75 MHz, CDCl₃) δ (ppm)139.2, 114.4, 77.7, 77.2, 76.8, 33.9, 32.3, 29.9, 29.0, 28.9. ElementalAnalysis: calcd for C₁₆H₃₀S, C: 75.52, H: 11.88, S: 12.60; found C:75.49, H: 11.84, S: 12.67.

Bis(pent-4-en-1-yl)sulfide. Yield 85%. ¹H NMR (CDCl₃): δ (ppm) 5.77-5.87(m, 2H), 4.94-5.08 (m, 4H), 2.49-2.57 (t, 4H), 2.17-2.25 (q, 4H),1.81-1.76 (m, 4H); ¹³C NMR (CDCl₃): δ (ppm) 29.03, 31.63, 33.06, 115.31,138.03. Elemental Analysis: calcd for C₁₀H₁₈S, C: 70.52, H: 10.65, S:18.82; found C: 70.49, H: 10.70, S: 18.73.

Monomer Synthesis

Bis(undec-10-en-1-yl)sulfone. To a 50 mL round bottom flask 15.0 g(0.044 mols) of bis(undec-10-en-1-yl)sulfide, 10 mL of distilled water,and 1.5 g (0.1 eq.) of hexachlorophosphazene were added and stirred at0° C. A 13 mL (0.130 mols) aliquot of 30% hydrogen peroxide was addeddropwise and the reaction mixture was allowed to warm to roomtemperature. The reaction mixture was stirred for 30 mins, at whichpoint a white solid formed. The reaction was extracted with ethylacetate (4×25 mL). The organic layer was dried over magnesium sulfatebefore removal of the solvent. The crude sulfone was recrystallized fromethanol and subsequently passed through a silica plug using ahexanes:ethyl acetate (9:1) eluent. Yield: 15.77 g, 96%. ¹H NMR (300MHz, CDCl₃): δ (ppm) 5.70-5.84 (m, 2H), 4.87-4.99 (m, 4H), 2.89 (t, 4H),1.96-2.03 (m, 4H), 1.74-1.84 (m, 4H), 1.17-1.43 (m, 24H); 13C NMR (75MHz, CDCl₃) δ (ppm) 139.4, 114.4, 77.7, 77.2, 76.8, 52.9, 34.0, 29.6,29.4, 29.3, 29.1, 28.7, 22.2. HRMS (ESI) (m/z): (M+H)+ calcd forC₂₂H₄₂O₂S 371.2978; found 371.2983. Elemental Analysis: calcd forC₂₂H₄₂O₂S, C: 71.29, H: 11.42, S: 8.65; found C: 71.58, H: 11.48, S:8.50.

In like manner, the procedure described above was used for the synthesisof bis(oct-7-en-1-yl)sulfone and bis(pent-4-en-1-yl)sulfone as well.

Bis(oct-7-en-1-yl)sulfone Yield 79%. ¹H NMR (300 MHz, CDCl₃): δ (ppm)5.68-5.82 (m, 2H), 4.89-4.99 (m, 4H), 2.91 (t, 4H), 1.97-2.07 (m, 4H),1.74-1.85 (m, 4H), 1.27-1.46 (m, 12H); 13C NMR (75 MHz, DMSO) δ (ppm)139.4, 115.4, 52.2, 40.7, 40.5, 40.2, 39.9, 39.6, 39.4, 33.7, 28.7,28.2, 21.9.HRMS (ESI) (m/z): (M+H)+ calcd for C₁₆H₃₀O₂S 287.2039; found287.2037. Elemental Analysis: calcd for C₁₆H₃₀O₂S, C: 67.08, H: 10.56,S: 11.19; found C: 65.42, H: 10.33, S: 10.82.

Bis(pent-4-en-1-yl)sulfone. Yield 92%. ¹H NMR (300 MHz, CDCl₃): δ (ppm)5.69-5.82 (m, 2H), 5.03-5.11 (m, 4H), 2.93 (t, 4H), 2.18-2.25 (m, 4H),1.74-1.85 (m, 4H); ¹³C NMR (75 MHz, CDCl₃) δ (ppm) 135.8, 116.1, 76.9,76.5, 76.1, 51.6, 31.7, 20.6. HRMS (ESI) (m/z): (M+H)+ calcd forC10H18O2S 203.1100; found 203.1101. Elemental Analysis: calcd forC10H18O2S, C: 59.37, H: 8.97, S: 15.85; found C: 59.28, H: 9.06, S:15.59.

Bis(pent-4-en-1-yl)sulfone alternate synthesis. Sodiumhydroxymethylsulfinate (2.0 g, 16.8 mmol), potassium carbonate (23 g,166 mmol), tetrabutylammonium bromide (0.40 g, 1.68 mmol) and5-bromo-1-pentene (5.0 g, 33.6 mmol) were suspended in a 2:1 DMF:watermixture (200 ml). The suspension was stirred for 72 hours at roomtemperature. The reaction was quenched with cold water (50 ml). Theaqueous suspension was then extracted with dichloromethane (50 ml) threetimes. The organic portion was isolated and washed with water threetimes. The organic was again isolated and dried over anhydrous magnesiumsulfate. Solids were removed via filtration and solvent was removedunder vacuum. The crude product was isolated by column chromatographyover silica gel using a 9:1 Hexane:ethyl acetate mixture as eluent.

Polymerization Procedures

Polymerization of Bis(undec-10-en-1-yl)sulfone. To a dry 50 mL Schlenktube containing a stir bar was added a 2M solution of 1.0 g of monomer(2.7 mmols) in dichloromethane. The solution was subjected to multiplefreeze-pump-thaw cycles until no visible gases were expelled from thesolution. Before the final thaw, 1 mol % Grubbs' First Generationcatalyst was added to the flask, and the vessel was equipped with areflux condenser and argon flow adapter. The apparatus was evacuated andpurged with argon before refluxing for 72 hours. After the allottedpolymerization time, the polymer precipitated from solution. Ethyl vinylether and tetrachloroethane were added to quench the polymerization anddissolve the polymer. The polymer was precipitated from cold methanol,filtered, collected, and dried under vacuum before characterization. ¹HNMR (300 MHz, C₂D₂Cl₄) δ (ppm) 5.89-5.76 (m, 2H), 5.40-5.30 (m, 2H),5.03-4.92 (m, 4H), 2.94-2.89 (t, 4H), 2.05-1.93 (m, 4H), 1.84-1.69 (m,4H), 1.46-1.28 (m, 24H); ¹³C NMR (75 MHz, C₂D₂Cl₄) δ 139.1, 130.2,129.8, 114.2, 52.5, 33.6, 32.5, 29.5, 29.2, 29.1, 28.9, 28.3, 27.1,21.8. FT-IR (ATR) v in cm⁻¹ 2918, 2847, 1461, 1414, 1327, 1274, 1248,1225, 1123, 1098, 964, 909, 774, 724, 603.

Polymerization of Bis(oct-7-en-1-yl)sulfone. ¹H NMR (300 MHz, C₂D₂Cl₄) δ(ppm) 5.44-5.37 (m, 2H), 2.95-2.89 (t, 4H), 2.00-1.95 (m, 4H), 1.84-1.71(m, 4H), 1.47-1.25 (m, 12H); ¹³C NMR (75 MHz, C₂D₂Cl₄) δ (ppm) 130.5,74.5, 74.2, 73.8, 52.9, 32.6, 29.4, 28.6, 22.2. FT-IR (ATR) v in cm-12918, 2849, 1459, 1412, 1326, 1274, 1249, 1203, 1122, 1082, 965, 773,727, 668, 602.

Polymerization of Bis(pent-4-en-1-yl)sulfone. ₁H NMR (300 MHz, CDCl₃) δ(ppm) 5.53-5.38 (m, 2H), 3.01-2.87 (t, 4H), 2.26-2.14 (m, 4H), 1.95-1.82(m, 4H); ¹³C NMR (75 MHz, CDCl₃) δ (ppm) 131.4, 75.6, 75.2, 74.9, 53.4,32.4, 22.9. FT-IR (ATR) v in cm⁻¹ 2942, 2860, 1451, 1412, 1321, 1275,1235, 1119, 1078, 1017, 965, 841, 774, 742, 703.

Hydrogenation of Unsaturated Polysulfones

Poly((eicosanyl)sulfone). Similar to a literature procedure, 250 mg ofpoly((eicos-10-en-yl)sulfone) was suspended in 20 mL of anhydrousm-xylene. Next, 0.9 g (3 eq.) of p-toluenesulfonylhydrazide (TSH) and 1mL of tripropylamine (TPA) was added to the flask. The reaction wasallowed to reflux for 3.5 hours, after which an additional 3 eq. TSH andTPA was added. The reaction was again refluxed for 3.5 hours and thencondensed to half the original volume before being precipitated intocold methanol. The polymers were filtered and dried under high vacuum.¹H NMR (300 MHz, C₂D₂Cl₄) δ (ppm) 2.95-2.89 (t, 4H), 1.78-1.74 (m, 4H),1.61 (m, 4H), 1.41-1.18 (m, 24H); FT-IR (ATR) v in cm⁻¹ 2916, 2846,1462, 1413, 1327, 1292, 1270, 1246, 1216, 1123, 1092, 774, 724.

Poly((dodecanyl)sulfone). ¹H NMR (300 MHz, C₂D₂Cl₄) δ (ppm) 2.95-2.89(t, 4H), 1.81-1.66 (m, 4H), 1.61 (m, 4H), 1.44-1.26 (m, 12H); 13C NMR(75 MHz, C₂D₂Cl₄) δ (ppm) 52.9, 29.8, 29.5, 28.7, 22.2. FT-IR (ATR) v incm⁻¹ 2916, 2846, 1461, 1413, 1326, 1300, 1267, 1239, 1197, 1123, 1072,988, 802, 774, 742, 725.

Poly((octanyl)sulfone). ¹H NMR (300 MHz, C₂D₂Cl₄) δ (ppm) 2.95-2.90 (t,4H), 1.85-1.75 (m, 4H), 1.48 (m, 4H), 1.46-1.32 (m, 4H); ¹³C NMR (75MHz, C₂D₂Cl₄) δ (ppm) 75.6, 75.3, 74.9, 54.0, 30.1, 29.7, 23.2. FT-IR(ATR) v in cm^(—1) 2936, 2846, 1459, 1412, 1324, 1271, 1224, 1193, 1120,1011, 775, 745, 728.

General Properties and Utilities of the Polymers According to VariousEmbodiments

Precision polysulfones in both crosslinked an uncrosslinked states mayhave utility in a variety of applications.

The polymers may be utilized as membranes for solid-oxide fuel cells,flow batteries, hydrogen pumping, membranes for ion conductivity,membranes for medical use (aliphatic rather than aromatic polysulfones),and other various applications.

The polymers may be utilized as fibers including hollow fibers, highmodulus fibers, and other various applications.

The polymers may be utilized as coatings for various applications. Thepolymers may be applied as paints or coatings in an uncured anduncrosslinked stated and may be cured or crosslinked once applied.

The polymers may be utilized in a variety of medical applications,including in catheters, stents, and other various applications.

The polymers may be utilized in film wrap, plastic bags, electricalinsulation, toys, pipes, siding, flooring, seat covers, packaging, latexpaints, adhesives, aircraft applications, automotive applications,additives for blending to alter existing polymers

The polymers may provide superior or improved barrier properties,hardness, tensile strength, creep or time dependent behavior, corrosionresistance, resistance to environmental stress cracking, toughness,strength/modulus to weight ratio, transparency, thermosettingproperties, shape memory properties, and others.

The polymers may be useful in “smart” materials that are responsive tothe environment to which they are exposed.

All patents, patent applications, provisional applications, andpublications referred to or cited herein are incorporated by referencein their entirety, including all figures and tables, to the extent theyare not inconsistent with the explicit teachings of this specification.

It should be understood that the examples and embodiments describedherein are for illustrative purposes only and that various modificationsor changes in light thereof will be suggested to persons skilled in theart and are to be included within the spirit and purview of thisapplication.

We claim:
 1. A component comprising a polysulfone, the polysufone havinga multiplicity of sulfone units separated by alkylene units in a polymerchain or a copolymer chain, and a crosslinking unit comprising areaction product of either: an ethylene unit with a diacrylate or adithiol; or an epoxy unit with a diol or a diamine, the epoxy unit beingderived from an ethenylene unit.
 2. The component according to claim 1,wherein the alkylene units are of the same mass and/or structure.
 3. Thecomponent according to claim 1, wherein the alkylene units are of atleast three different mass and/or structure.
 4. The component accordingto claim 1, wherein the alkylene unit is a C₄ to C₃₆ unit.
 5. Thecomponent according to claim 1, wherein the alkylene unit consists of amultiplicity of methylene units.
 6. The component according to claim 1,where at least one of the alkylene units further comprises an ethenyleneunit separated from the sulfone units by at least one methylene unit. 7.The component according to claim 6, wherein each of the alkylene unitsconsists of the ethenylene unit separated from the sulfone units by atleast one methylene unit.
 8. The component according to claim 1, whereinthe component is a fuel cell.
 9. The component according to claim 1,wherein the component is a flow battery.
 10. The component according toclaim 1, wherein the component is a membrane.
 11. The componentaccording to claim 1, wherein the component is a fiber.
 12. Thecomponent according to claim 1, wherein the component is a paint or acoating.